CN105431959B - Battery case surface treated steel plate, battery case and battery - Google Patents
Battery case surface treated steel plate, battery case and battery Download PDFInfo
- Publication number
- CN105431959B CN105431959B CN201480043048.9A CN201480043048A CN105431959B CN 105431959 B CN105431959 B CN 105431959B CN 201480043048 A CN201480043048 A CN 201480043048A CN 105431959 B CN105431959 B CN 105431959B
- Authority
- CN
- China
- Prior art keywords
- steel plate
- battery case
- battery
- surface treated
- treated steel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 201
- 239000010959 steel Substances 0.000 title claims abstract description 201
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 166
- 239000010410 layer Substances 0.000 claims abstract description 144
- 238000007747 plating Methods 0.000 claims abstract description 61
- 239000013078 crystal Substances 0.000 claims abstract description 50
- 239000002344 surface layer Substances 0.000 claims abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 163
- 239000000956 alloy Substances 0.000 claims description 163
- 238000012545 processing Methods 0.000 claims description 15
- 238000004381 surface treatment Methods 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 123
- 238000010438 heat treatment Methods 0.000 abstract description 45
- 229910052742 iron Inorganic materials 0.000 abstract description 32
- 230000006399 behavior Effects 0.000 abstract description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 195
- 238000000576 coating method Methods 0.000 description 126
- 239000011248 coating agent Substances 0.000 description 124
- 229910052759 nickel Inorganic materials 0.000 description 75
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 36
- 238000000034 method Methods 0.000 description 34
- 238000009792 diffusion process Methods 0.000 description 25
- 238000011156 evaluation Methods 0.000 description 24
- 229910052748 manganese Inorganic materials 0.000 description 20
- 239000011572 manganese Substances 0.000 description 20
- 239000000203 mixture Substances 0.000 description 20
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 19
- 239000007789 gas Substances 0.000 description 19
- 238000000137 annealing Methods 0.000 description 16
- 238000004090 dissolution Methods 0.000 description 16
- 235000019589 hardness Nutrition 0.000 description 16
- 238000005259 measurement Methods 0.000 description 12
- 238000012797 qualification Methods 0.000 description 12
- 230000005611 electricity Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 7
- 150000002815 nickel Chemical class 0.000 description 7
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000001887 electron backscatter diffraction Methods 0.000 description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 5
- 208000037656 Respiratory Sounds Diseases 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- 238000004611 spectroscopical analysis Methods 0.000 description 5
- 229910000990 Ni alloy Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 4
- 229940124530 sulfonamide Drugs 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000004033 diameter control Methods 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229950000244 sulfanilic acid Drugs 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910000655 Killed steel Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910018095 Ni-MH Inorganic materials 0.000 description 2
- 229910018477 Ni—MH Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- XQBCZVOLPUGXRL-UHFFFAOYSA-N methanesulfonic acid;nickel Chemical compound [Ni].CS(O)(=O)=O XQBCZVOLPUGXRL-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 239000010731 rolling oil Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/011—Layered products comprising a layer of metal all layers being exclusively metallic all layers being formed of iron alloys or steels
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/117—Inorganic material
- H01M50/119—Metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
- H01M50/1245—Primary casings; Jackets or wrappings characterised by the material having a layered structure characterised by the external coating on the casing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
- H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
- H01M50/128—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
- H01M50/133—Thickness
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Electroplating Methods And Accessories (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The present invention provides a kind of battery case with surface treated steel plate (100), it is characterized in that, implementation heat treatment forms after the battery case implements iron-nickel alloy plating with surface treated steel plate (100) on steel plate (10), wherein, most surface layer is layer of iron-nickel alloy (20), and the average crystal grain diameter of the most surface of the layer of iron-nickel alloy (20) is 1 μm~8 μm.Using the present invention, being capable of providing can inhibit the iron of inside battery to dissolve out when as battery case, thus enable that battery long lifetime, and the battery case and battery for improving the battery case surface treated steel plate of the battery behaviors such as flash-over characteristic, being obtained using the battery case with surface treated steel plate.
Description
Technical field
Hold the present invention relates to battery case surface treated steel plate, using the battery of the battery case surface treated steel plate
Device and the battery using the battery case.
Background technology
In recent years, in all respects using the movement equipment such as audio frequency apparatus, mobile phone, working power is mostly using work
Alkaline battery for one-shot battery, the Ni-MH battery as secondary cell, lithium ion battery etc..With the high property of the equipment of carrying
Energyization, this battery are also required to long lifetime and high performance etc., filled with by positive active material, negative electrode active material etc.
The battery case of the generating element of composition also serves as the important structural detail of battery and is required to improve its performance.
As the battery case, such as Patent Document 1 discloses a kind of shapes after foring nickel coating on the steel plate
Into Fe-Ni alloy coating, the battery that machine-shaping forms in a manner that the Fe-Ni alloy layer becomes battery case inner surface holds
Device.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2000-123797 bulletins
Invention content
Problems to be solved by the invention
But in the battery case disclosed in above patent document 1, formed by implementing Fe-Ni alloy plating
There are the non-crystal part that many iron are easy to dissolution in the surface of Fe-Ni alloy coating, if this material is used as battery
Container is possible to dissolve out iron from amorphous parts in the electrolytic solution, the gas generated with the dissolution of iron and in inside battery as a result,
Cognition causes battery case damaged, and so as to which leakage occur, the service life as battery will shorten.
It, can when being used as battery case the object of the present invention is to provide a kind of battery case surface treated steel plate
Inhibit the iron dissolution of inside battery, thus enable that battery long lifetime, and improve the battery behaviors such as flash-over characteristic.This
Outside, the present invention also aims to provide a kind of battery case obtained by using the battery case with surface treated steel plate
And battery.
The solution to the problem
In order to achieve the above object, the inventors of the present invention by it is concentrating on studies as a result, find implement iron-nickel on the steel plate
It is heat-treated after plating, the average crystal grain diameter of the most surface of Fe-Ni alloy layer being formed in most surface is set as 1 μm
~8 μm, thus, it is possible to reach above-mentioned purpose, complete the present invention.
That is, according to the present invention, it is possible to provide a kind of battery case surface treated steel plates, which is characterized in that the battery holds
Implementation heat treatment forms after device implements Fe-Ni alloy plating with surface treated steel plate on the steel plate, wherein, most surface layer
It is Fe-Ni alloy layer, the average crystal grain diameter of the most surface of the Fe-Ni alloy layer is 1 μm~8 μm.
The battery case of the present invention is preferably with surface treated steel plate, and the Fe of the most surface of the Fe-Ni alloy layer is former
The content ratio of son is the atom % of 12 atom %~50.
The battery case of the present invention is preferably with surface treated steel plate, the Vickers hardness (HV) of the Fe-Ni alloy layer
It is 210~250.
Any of the above-described kind of battery case is subjected to processing and forming with surface treated steel plate according to the present invention, it is possible to provide a kind of
The battery case formed.
In addition, according to the present invention, it is possible to provide a kind of batteries formed using above-mentioned battery case.
The effect of invention
In accordance with the invention it is possible to the battery case surface treated steel plate provided can inhibit when as battery case
The dissolution of the iron of inside battery thus enables that battery long lifetime, and improves the battery behaviors such as flash-over characteristic, in addition,
It also is able to provide the battery case and battery obtained with surface treated steel plate using the battery case.
Description of the drawings
Fig. 1 is the structure chart of the battery case surface treated steel plate of the 1st embodiment.
Fig. 2 is the battery case table represented by high frequency glow discharge emission spectrophotometer to the 1st embodiment
The figure of the result of surface treatment measurement of the steel plate Ni intensity and Fe intensity.
Fig. 3 is the structure chart of the battery case surface treated steel plate of the 2nd embodiment.
Fig. 4 is the figure for illustrating the method for the battery case surface treated steel plate for manufacturing the 2nd embodiment.
Fig. 5 is the battery case table represented by high frequency glow discharge emission spectrophotometer to the 2nd embodiment
The figure of the result of surface treatment measurement of the steel plate Ni intensity and Fe intensity.
Fig. 6 is the structure chart of another example of the battery case surface treated steel plate for representing the 2nd embodiment.
Fig. 7 is the battery case table represented by high frequency glow discharge emission spectrophotometer to the 2nd embodiment
Another example of surface treatment steel plate measures the figure of the result of Ni intensity and Fe intensity.
Fig. 8 is the figure for illustrating the method for the battery case surface treated steel plate for manufacturing the 3rd embodiment.
Fig. 9 is to represent to be surface-treated the battery case of embodiment by high frequency glow discharge emission spectrophotometer
The figure of the result of measurement of the steel plate Ni intensity and Fe intensity.
Specific embodiment
Hereinafter, illustrate embodiments of the present invention with reference to the accompanying drawings.
1st embodiment
Fig. 1 is the figure of the structure for the battery case surface treated steel plate 100 for representing present embodiment.As shown in Figure 1, this
The battery case of the embodiment surface treated steel plate that surface treated steel plate 100 is battery case, by steel plate 10
On implement and implement the heat treatments such as continuous annealing, box annealing after Fe-Ni alloy plating, Fe-Ni alloy layer 20 is consequently formed
It forms.
10 ＞ of ＜ steel plates
As the steel plate 10 of the substrate of surface treated steel plate 100 of the battery case as present embodiment, as long as it draws
Deep processing, thinning drawing processing are using the material of drawing process and the excellent in workability of the processing (DTR) of replication processing
Can, it is not particularly limited, but the low-carbon aluminium deoxidation killed steel (weight of 0.01 weight % of carbon amounts~0.15 for example may be used
Amount %), the ultra-low carbon steel that carbon amounts is below 0.003 weight % or the non-timeliness that Ti, Nb etc. are formed is added into ultra-low carbon steel
Property ultra-low carbon steel.
In the present embodiment, it is used as substrate：Pickling is carried out to the hot rolled plate of these steel and removes surface
Oxide skin (oxidation film), carries out cold rolling later, the material that then electrolytic cleaned ROLLING OIL forms；Alternatively, in the electrolytic cleaned
It is annealed later, the material that temper rolling forms.In this case annealing can be in continuous annealing or box annealing
It is any, be not particularly limited.
20 ＞ of ＜ Fe-Ni alloys layer
As shown in Figure 1, Fe-Ni alloy layer 20 is the layer on the most surface layer as battery case surface treated steel plate 100,
Implement the heat treatment such as continuous annealing, box annealing after Fe-Ni alloy plating by being implemented on steel plate 10 and formed, most
The average crystal grain diameter on surface is controlled in the range of 1 μm~8 μm.
In the present embodiment, it is heat-treated after Fe-Ni alloy plating by being implemented on steel plate 10, Neng Goushi
Locality crystallizes Fe-Ni alloy layer 20, and by the way that the average crystal grain diameter control of the most surface of Fe-Ni alloy layer 20 is existed
In above range, the hardness that can make the surface of Fe-Ni alloy layer 20 is appropriate, and obtained battery case is surface-treated
When steel plate 100 is used as battery case, iron dissolution can be inhibited the phenomenon that electrolyte.Therefore, in the present embodiment, as
During battery case, iron dissolution can be inhibited to electrolyte, therefore can prevent the gas generated by the dissolution with iron from causing
Battery case is damaged, and the anti-leakage by promoting battery case, and it is possible to realize the long lifetimes of battery.In addition, at this
In embodiment, by making the hardness on surface of Fe-Ni alloy layer 20 appropriate, when being shaped to battery case, Fe-Ni alloy layer
20 become battery case inner surface, in the case where implementing the processing such as drawing, thinned, DI or DTR moldings, can be closed in iron-nickel
The surface of layer gold 20 generates fine and shallower depth crackle.Moreover, crackle fine by this and shallower depth, can increase
The internal resistance decline of the contact area of anode mixture used by Fe-Ni alloy layer 20 and battery, as a result, battery, Neng Gouti
The battery behaviors such as lifting electrical characteristics.
On the other hand, in the case of without above-mentioned heat treatment, there are it is following the problem of.That is, it is closed implementing iron-nickel
The problem of battery case it is iron obtained from carrying out processing and forming to the steel plate that is not heat-treated after golden plating
Electrolyte can be dissolved out, the lost of life as battery.In addition, the reason of being dissolved out as this iron and it is contemplated that for example,
In the state of not being heat-treated, deformed in the remained on surface of the layer formed by Fe-Ni alloy plating, and this deformation causes
Will largely there be the non-crystal part for being easy to dissolution as iron.
In addition, if the average crystal grain diameter of the most surface of Fe-Ni alloy layer 20 is too small, the hardness of Fe-Ni alloy layer 20
Become excessively high, when carrying out processing and forming as battery case, in Fe-Ni alloy layer 20, generate arrival the deeper of steel plate 10 and split
Line can expose so as to steel plate 10.In this case, iron will be dissolved out from the part of the exposure of steel plate 10, by with the dissolution of iron
And the gas breakage battery case generated, the anti-leakage of battery case can reduce.If the alternatively, most table of Fe-Ni alloy layer 20
The average crystal grain diameter in face is excessive, then the hardness of Fe-Ni alloy layer 20 becomes too low.When processing and forming is battery case, no
Battery case inner surface can be made suitably to crack, therefore, it is impossible to which fully obtaining reduces the internal resistance of battery and promote battery
The effect of characteristic.
In addition, in the present embodiment, such as the most surface of Fe-Ni alloy layer 20 can be measured by following method
Average crystal grain diameter.That is, when scanning type electricity Xian Wei Mirror (SEM) is used to irradiate electron ray to Fe-Ni alloy layer 20, parsing
By by the surface of Fe-Ni alloy layer 20 reflect Lai electron ray project to screen obtained from electronics backscattering pattern
(EBSD (Electron Backscatter Diffraction)), so as to for each crystal grain for forming Fe-Ni alloy layer 20
The information of crystal grain diameter is obtained, thus calculates average crystal grain diameter.It is in particular, anti-for the surface by Fe-Ni alloy layer 20
It penetrates for the electron ray come, by the reflection angle difference between adjacent point of irradiation in prescribed limit (such as 2 °~15 °)
Region is handled as a crystal grain, and thus, it is possible to be directed to each crystal grain to measure crystal grain diameter, and can equal these results
Calculate average crystal grain diameter.
In the present embodiment, the average crystal grain diameter of the most surface of Fe-Ni alloy layer 20 is 1 μm~8 μm, preferably 2 μ
M~8 μm.It, will be by above-mentioned by the way that the average crystal grain diameter of the most surface of Fe-Ni alloy layer 20 is controlled within the above range
When the battery case that mode obtains is used as battery case with surface treated steel plate 100, anti-leakage and battery behavior can be promoted.
In addition, when measuring average crystal grain diameter, using the method for parsing above-mentioned electronics backscattering pattern (EBSD)
In the case of, obtained measured value represents the average crystal grain diameter of most surface for Fe-Ni alloy layer 20.In contrast, at this
In embodiment, due to also conducting heat to the inside of Fe-Ni alloy layer 20 by above-mentioned heat treatment, it is therefore contemplated that crystallization
Change is suitably performed to inside, it is believed that not only in the most surface of Fe-Ni alloy layer 20, average crystal grain diameter is near most surface
Within the above range.
In addition, in the present embodiment, the hardness on the surface of Fe-Ni alloy layer 20 is preferably 210 by Vickers hardness (HV)
~250, more preferably 220~240.If the Vickers hardness on the surface of Fe-Ni alloy layer 20 is excessively high, as battery case into
During row processing and forming, deeper crackle is generated in Fe-Ni alloy layer 20 and steel plate 10 exposes, as a result, as battery case
In the case of, iron will be dissolved out from the part of the exposure of steel plate 10, and anti-leakage can reduce.On the other hand, if Fe-Ni alloy layer
The Vickers hardness on 20 surface is too low, then when carrying out processing and forming as battery case, it is impossible to make battery case inner surface appropriate
Ground cracks, therefore, it is impossible to the effect for fully obtaining the internal resistance for reducing battery and promoting battery behavior.
The thickness of Fe-Ni alloy layer 20 is not particularly limited, but preferably 0.5 μm~3.0 μm, more preferably
1.0 μm~2.0 μm.By the way that the thickness of Fe-Ni alloy layer 20 is set within the above range, at obtained battery case surface
When managing steel plate 100 and being used as battery case, the anti-leakage and battery behavior of battery case obtain further up.
In addition, the thickness of Fe-Ni alloy layer 20 can be for example measured by the following method.That is, it is put by high frequency glow
Electroluminescence spectroscopy apparatus measures Ni with surface treated steel plate 100 to battery case to the depth direction of Fe-Ni alloy layer 20
Since the passage of intensity detect the depth until there is no nickel measuring, so as to acquire the thickness of Fe-Ni alloy layer 20
Degree.
At this point, in the present embodiment, when will measure Ni intensity to battery case surface treated steel plate 100, Ni
On the basis of the maximum value of intensity, more than 1/10 region that Ni intensity is maximum value can be set as to the region there are nickel.Therefore,
In the present embodiment, Ni intensity is measured in the depth direction for battery case surface treated steel plate 100, is started with measuring
At the time of be starting point, calculate Ni intensity become less than Ni intensity maximum value 1/10 at the time of until time of measuring, can
Time of measuring according to calculating acquires the thickness of Fe-Ni alloy layer 20.
Here, Fig. 2 is represented through high frequency glow discharge emission spectrophotometer to battery case surface treated steel
The depth direction of plate 100 to Fe-Ni alloy layer 20 measures the chart of the result of the passage of Ni intensity and Fe intensity.In addition,
In Fig. 2, horizontal axis represents the time of measuring of high frequency glow discharge emission spectrophotometer, the longitudinal axis Ni intensity measured of expression or
Fe intensity.For example, in chart shown in Fig. 2, the value at the time of maximum value of Ni intensity is about 70sec can be by Ni intensity
(being at the time of expression with " Ni intensity 1/10 " in fig. 2) is calculated as opening from measurement at the time of becoming less than the 1/10 of the maximum value
At the time of beginning about 105sec, thereby, it is possible to the thickness of Fe-Ni alloy layer 20 is acquired according to the time of measuring of about 105sec calculated
Degree.
The manufacturing method ＞ of ＜ battery cases surface treated steel plate 100
Then, illustrate the manufacturing method of the battery case surface treated steel plate 100 of present embodiment.
First, prepare the steel plate for forming steel plate 10, implement Fe-Ni alloy plating on steel plate 10.Fe-Ni alloy plates
Apply for example can be by carrying out, but putting down from easily controllable obtained Fe-Ni alloy layer 20 the methods of electrolysis plating, chemical plating
From the aspect of equal crystal grain diameter is such, preferably carried out by being electrolysed plating.
For example, in the case of by being electrolysed plating progress Fe-Ni alloy plating, can be formed by using in addition to containing
Plating is implemented in plating bath (iron-nickel plating bath) except the molysite and nickel salt of Fe-Ni alloy layer 20 also containing buffer etc. on steel plate 10
It applies to carry out.Specific example as iron-nickel plating bath, which can be included, bathes watt, is added to sulphur based on sulfanilamide (SN) acid bath etc.
Plating bath that the buffers such as the nickel salts such as the molysite such as sour iron, nickel sulfate, nickel chloride, boric acid, citric acid form etc..
In addition, the molysite contained by iron-nickel plating bath and nickel salt are not particularly limited, however, as molysite, preferably
For ferric sulfate, iron chloride, sulfanilic acid iron, ironic citrate, in addition, as nickel salt, preferably nickel sulfate, nickel chloride, nickelous carbonate, vinegar
Sour nickel, sulfanilic acid nickel, methanesulfonic acid nickel.In addition, in the present embodiment, in order to by the surface of Fe-Ni alloy layer 20 formed
Vickers hardness is set within the above range, and molysite and nickel salt are preferably using other metals contained substantially no in addition to iron and nickel
Substance.But as molysite and nickel salt, only as the degree of impurity, then other metals can also be contained.
In the present embodiment, for the content of Fe atoms and Ni atoms ratio in the layer that is formed by Fe-Ni alloy plating,
It is not particularly limited, however, the content of Fe atoms is than being preferably 15 atom %~45 atom %, more preferably 20 atom %
~40 atom %.In addition, the content of Ni atoms is than being preferably 55 atom %~85 atom %, more preferably 60 atom %~80 former
Sub- %.It, can be by obtained Fe-Ni alloy layer 20 most by the way that the content of Fe atoms and Ni atoms ratio is set within the above range
The average crystal grain diameter control on surface is within the above range.In addition, it can be controlled by suitably adjusting the composition of iron-nickel plating bath
Make the content ratio of the Fe atoms and Ni atoms.If the content of Fe atoms is than excessive (i.e. the content of Ni atoms is than very few), iron-nickel
The average crystal grain diameter of the most surface of alloy-layer 20 becomes too small, on the other hand, if the content of Fe atoms is than very few (i.e. Ni atoms
Content than excessive), then the average crystal grain diameter of the most surface of Fe-Ni alloy layer 20 becomes too much.
In addition, the pH of iron-nickel plating bath is preferably 1.0~3.0, more preferably 1.5~2.9.By by the pH of iron-nickel plating bath
If within the above range, can prevent from generating the sludge (sediment) of iron system in iron-nickel plating bath, thereby, it is possible to prevent sludge
It is attached on steel plate 10, moreover, because the concentration of the iron ion in iron-nickel plating bath can suitably be managed, therefore, it is possible to good
Ground carries out Fe-Ni alloy plating.
Also, the bath temperature of iron-nickel plating bath is preferably 40 DEG C~80 DEG C, more preferably 50 DEG C~70 DEG C.In addition, by iron-
The current density that nickel plating bath implements when electrolysis is electroplated is preferably 5A/dm2~40A/dm2, more preferably 5A/dm2~30A/dm2.It is logical
Cross will carry out electrolysis plating when iron-nickel plating bath bath temperature and current density set within the above range, can carry out well iron-
Nickel alloy plating.
Then, in the present embodiment, implement heat treatment on the steel plate 10 for implement Fe-Ni alloy plating.Lead to as a result,
It crosses and carries out thermal diffusion using the layer that Fe-Ni alloy plating is formed on steel plate 10, so as to form Fe-Ni alloy layer 20.It is in addition, right
The methods of being not particularly limited in heat-treating methods, such as continuous annealing, box annealing may be used.By continuous
In the case that annealing is heat-treated, it is preferably set to heat treatment temperature：700 DEG C~800 DEG C, heat treatment time：10 seconds~300
Second, moreover, in the case where being heat-treated by box annealing, it is preferably set to heat treatment temperature：450 DEG C~650 DEG C, heat at
Manage the time：1 hour~10 hours, heat-treating atmosphere：Non-oxidizing atmosphere or restitutive protection's gas atmosphere.In addition, will be hot
In the case that processing atmosphere is set as restitutive protection's gas atmosphere, protective gas is preferably preferably referred to as richness using by heat conduction
The protective gas generation of ammonia crackle method, being made of -25% nitrogen of 75% hydrogen of hydrogen annealing.
Here, the condition of the heat treatment temperature, heat treatment time when being heat-treated by suitably adjusting, can control
The average crystal grain diameter of the most surface of Fe-Ni alloy layer 20.In particular, heat treatment temperature is set higher or makes hot place
The reason time is longer, then more can increase average crystal grain diameter, on the other hand, sets lower by heat treatment temperature or makes hot place
The reason time is shorter, then more can reduce average crystal grain diameter.
In the present embodiment, by being heat-treated, it can carry out suitably Fe-Ni alloy layer 20 as described above
Crystallization, can there is battery case obtained from the battery case obtained as a result, carries out processing and forming with surface treated steel plate 100
Effect ground inhibits iron dissolution to electrolyte.In contrast, in the case of without heat treatment, obtained surface treated steel plate is most
Surface amorphous parts can become more, and when as battery case, iron can be dissolved out from the amorphous parts into electrolyte.Particularly
In the case of without heat treatment, since the orientation of the crystal grain on surface is crooked (askew ん In い Ru), even if logical
In the case of crossing the measurement average crystal grain diameter such as electronics backscattering pattern (EBSD), it is irradiated to the reflection of the electron ray on surface
Angle also can deflection, cannot get electronics backscattering pattern (EBSD), average crystal grain diameter can not be calculated.In contrast, at this
It is crooked to eliminate this by implementing heat treatment after Fe-Ni alloy plating is implemented in embodiment, can suitably it make
The surface crystallization of the Fe-Ni alloy layer 20 of formation, can effectively inhibit the dissolution of iron.
In addition, the content ratio of the Fe atoms and Ni atoms in Fe-Ni alloy layer 20 is not particularly limited, most surface
The contents of Fe atoms is than being preferably the atom % of 12 atom %~50, the atom % of more preferably 15 atom %~45, further preferably
For the atom % of 20 atom %~40.It, can be by Fe-Ni alloy layer 20 by the way that the content ratio of Fe atoms is set within the above range
The average crystal grain diameter control of most surface is within the above range.Here, as by the Fe atoms of the most surface of Fe-Ni alloy layer 20
Content than setting method within the above range, for example, the molysite and nickel salt in above-mentioned adjustment iron-nickel plating bath can be included
Content than method.In addition, as the method for ratio for measuring the Fe atoms contained by Fe-Ni alloy layer 20, for example, can
The method for including the ratio for the Fe atoms that most surface is measured by sweep type auger electrons spectroscopy apparatus.
By above-mentioned mode, the battery case surface treated steel plate 100 of present embodiment can be manufactured.
Using the battery case surface treated steel plate 100 of present embodiment, as above, iron-nickel is implemented on steel plate 10
It is heat-treated after alloy plated, so as to suitably crystallize Fe-Ni alloy layer 20, moreover, by Fe-Ni alloy layer
The average crystal grain diameter of 20 most surface is controlled within the above range, as a result, in the battery case surface treated steel that will be obtained
When plate 100 is used as battery case, anti-leakage and battery behavior can be promoted.
＜ battery cases ＞
Pass through machine-shaping above-mentioned battery case surface treated steel plate 100, it will be able to obtain the battery of present embodiment
Container.In particular it is possible to by drawing, be thinned, DI or DTR are molded, by above-mentioned battery case with surface treated steel plate 100 into
Type is battery case shape, so as to obtain battery case.In addition, at this point, iron-nickel of battery case surface treated steel plate 100
Alloy-layer 20 becomes battery case inner surface side.
The battery case obtained in this way is to be formed by above-mentioned battery case with surface treated steel plate 100
, therefore, the battery behaviors such as anti-leakage and flash-over characteristic rise, as a result, other than battery life is grown, the electricity such as flash-over characteristic
Pond characteristic is also very excellent.Thus it is for example possible to function well as the electricity using the electrolyte of alkalinity such as alkaline battery, Ni-MH battery
The battery cases such as pond, lithium ion battery.
2nd embodiment
Then, illustrate the 2nd embodiment of the present invention.
The battery case of 2nd embodiment has structure shown in Fig. 3 with surface treated steel plate 100a, in Fe-Ni alloy
Iron-nickel diffusion layer 50 is equipped between layer 20a and steel plate 10, in addition to this, there is the battery case surface with the 1st embodiment
Handle 100 same structure of steel plate.
The battery case of 2nd embodiment is used with the battery case of surface treated steel plate 100a and above first embodiment
Surface treated steel plate 100 is different, is manufactured by following method.That is, first, by sequentially forming nickel on steel plate 10
Coating 40 and Fe-Ni alloy coating 30, obtain surface treated steel plate shown in Fig. 4.Secondly, surface treated steel shown in Fig. 4
Plate implements heat treatment, makes each layer thermal diffusion as a result, and forms Fe-Ni alloy layer 20a and iron-nickel diffusion layer 50, so as to make
Make battery case surface treated steel plate 100a.
Here, the Fe-Ni alloy coating 30 being formed on steel plate 10 can by with the iron of above first embodiment-
Plating is carried out under the conditions of nickel alloy plating is same and is formed, in addition, the nickel coating 40 being formed on steel plate 10 can be by adopting
It is bathed with watt, the well known method of sulfanilic acid acid bath etc. is formed.
In the present embodiment, implement heat treatment on surface treated steel plate shown in Fig. 4, thus make each layer thermal diffusion and
Fe-Ni alloy layer 20a and iron-nickel diffusion layer 50 are formed, but at this point, passes through nickel coating 40 and 30 thermal diffusion of Fe-Ni alloy coating
And Fe-Ni alloy layer 20a is formed, in addition, forming iron-nickel diffusion layer 50 by steel plate 10 and 40 thermal diffusion of nickel coating.Here,
When forming Fe-Ni alloy layer 20a and iron-nickel diffusion layer 50, nickel coating 40 is made to spread completely by heat treatment, as shown in figure 3,
The battery case made is not with remaining individual nickel coating 40 in surface treated steel plate 100a.
In addition, the condition to heat treatment is not particularly limited, the heat treatment with above first embodiment can be set as
Same condition, but heat treatment temperature and heat treatment time are adjusted, it is set as not remaining condition as individual nickel coating 40.
In the present embodiment, the thickness of the nickel coating 40 before heat treatment is preferably 1.5 μm hereinafter, more preferably 1.0 μm
Below.In the case that the thickness of nickel coating 40 before heat treatment is more than 1.5 μm, in order to which nickel coating is made to spread completely, it is possible to
The prolonged heat treatment of heat treatment temperature or needs in high temperature is needed, can there is a situation where to be deteriorated by thermally-induced steel plate.It is logical
It crosses and the thickness of the nickel coating 40 before heat treatment is set as 1.5 μm hereinafter, can inhibit the phenomenon that, by thermally-induced steel plate deterioration, to lead to
Cross further be set as 1.0 μm hereinafter, can by by heat treatment make nickel coating 40 completely spread when heat treatment temperature set more
It is low or heat treatment time can be set as shorter, the phenomenon that therefore, it is possible to prevent from being deteriorated by thermally-induced steel plate 10.
In addition, in the present embodiment, the size of the average crystal grain diameter of the most surface of Fe-Ni alloy layer 20a with it is above-mentioned
The Fe-Ni alloy layer 20 of the battery case of 1st embodiment surface treated steel plate 100 is similary.In addition, control iron-nickel is closed
The method of the average crystal grain diameter of the most surface of layer gold 20a is not particularly limited, but can for example include with it is above-mentioned
Implement the method for Fe-Ni alloy plating under the conditions of 1st embodiment is same, implement heat-treating methods.
Also, in the present embodiment, the hardness of Fe-Ni alloy layer 20a also with the battery case of above first embodiment
It is similary with the Fe-Ni alloy layer 20 of surface treated steel plate 100.
The thickness of Fe-Ni alloy layer 20a is not particularly limited, but preferably 0.1 μm~1.0 μm, more preferably
0.1 μm~0.5 μm.By the way that the thickness of Fe-Ni alloy layer 20a is set within the above range, the battery case surface that will be obtained
When handling steel plate 100a as battery case, anti-leakage and battery behavior are further enhanced.
In addition, in the present embodiment, such as can battery case surface treated steel plate be measured by the following method
The thickness of the Fe-Ni alloy layer 20a of 100a.That is, high frequency glow discharge is passed through for battery case surface treated steel plate 100a
When the depth direction of from emission spectrophotometer to Fe-Ni alloy layer 20a measure the passage of Ni intensity, it can detect from measurement
Start thickness of the depth until Ni intensity become the maximums as Fe-Ni alloy layer 20a.
Here, Fig. 5 is to represent to pass through high frequency glow discharge luminescence spectrometer for battery case surface treated steel plate 100a
The depth direction of from analytical equipment to Fe-Ni alloy layer 20a measure the chart of the result of the passage of Ni intensity and Fe intensity.Separately
Outside, in Figure 5, horizontal axis represents the time of measuring of high frequency glow discharge emission spectrophotometer, the Ni that longitudinal axis expression is measured
Intensity or Fe intensity.For example, in chart shown in Fig. 5, by Ni intensity become the maximums at the time of (uses " Ni intensity in Figure 5
At the time of maximum value " represents) at the time of be calculated as the about 45sec since measurement, thereby, it is possible to according to the about 45sec calculated
Time of measuring acquire the thickness of Fe-Ni alloy layer 20a.
In addition, in the present embodiment, Fe-Ni alloy layer 20a is by Fe-Ni alloy coating 30 and 40 thermal expansion of nickel coating
It dissipates and is formed, therefore, thickness is generally thicker than the thickness of Fe-Ni alloy coating 30.
In addition, in the present embodiment, the thickness of iron-nickel diffusion layer 50 is not particularly limited, however, with above-mentioned
Similarly, the thickness of iron-nickel diffusion layer 50 can also pass through high frequency glow discharge luminescence spectrometer to the thickness of Fe-Ni alloy layer 20a
Analytical equipment measures.That is, for battery case surface treated steel plate 100a, pass through high frequency glow discharge ICP Atomic Emission Spectrophotometer
Device measures the passage of Ni intensity to depth direction, and as the thickness of iron-nickel diffusion layer 50, can detect becomes most from Ni intensity
1/10 depth of maximum value is become less than at the time of big value to Ni intensity.
For example, in chart shown in Fig. 5, as described above, by since measuring to Ni intensity become the maximums, about
Depth until at the time of 45sec, as the thickness of Fe-Ni alloy layer 20a, also, will be from the Ni intensity become the maximums
At the time of becoming smaller than 1/10 about 85sec of maximum value at the time of about 45sec to Ni intensity (" Ni intensity 1/ is used in Figure 5
10 " represent at the time of) until depth, the thickness as iron-nickel diffusion layer 50.At this point, that according to from about 45sec at the time of
The time of measuring of about 40sec in during until at the time of about 85sec acquires the thickness of iron-nickel diffusion layer 50.
In the present embodiment, as shown in figure 3, by foring nickel coating 40 and Fe-Ni alloy coating on steel plate 10
Thermal diffusions are carried out after 30, also, make the size of the average crystal grain diameter of the most surface of Fe-Ni alloy layer 20a to be formed with it is upper
State that the 1st embodiment is similary, when obtained battery case is used as battery case with surface treated steel plate 100a, with the above-mentioned 1st
The battery case of embodiment similarly, can promote anti-leakage and battery behavior with surface treated steel plate 100.
In addition, present embodiment can also be following structure：By suitably adjusting the nickel coating 40a's before being heat-treated
Thickness, the condition of heat treatment, as battery case shown in fig. 6 is with surface treated steel plate 100b, in Fe-Ni alloy layer 20a
Individual nickel coating 40a is remained between iron-nickel diffusion layer 50.
In the battery case in surface treated steel plate 100b, such as can Fe-Ni alloy be measured by the following method
The thickness of layer 20a.That is, by high frequency glow discharge emission spectrophotometer, to battery case surface treated steel plate 100b
The passage of Fe intensity is measured to the depth direction of Fe-Ni alloy layer 20a, and is detected since measuring until there is no iron
Depth can acquire the thickness of Fe-Ni alloy layer 20a.
At this point, in the present embodiment, by it is when measuring Fe intensity with surface treated steel plate 100b for battery case,
Fe intensity is set as the region there are iron by the maximum value of Fe intensity as benchmark in more than 1/10 region of maximum value.Therefore,
In the present embodiment, Fe intensity is measured in the depth direction with surface treated steel plate 100b for battery case, is opened with measuring
For starting point at the time of beginning, the time of measuring until calculating at the time of Fe intensity becomes less than the 1/10 of maximum value for the first time, Neng Gougen
The thickness of Fe-Ni alloy layer 20a is acquired according to the time of measuring calculated.In addition, the maximum value of Fe intensity is represented through high frequency brightness
Light Discharge illuminating spectroscopy apparatus is measured to the battery case depth direction of surface treated steel plate 100b until reaching steel plate
Fe intensity until 10, when Fe intensity and Ni intensity do not change.
Here, Fig. 7 is to represent to be surface-treated battery case by high frequency glow discharge emission spectrophotometer
The depth direction of from steel plate 100b to Fe-Ni alloy layer 20a measure the chart of the result of the passage of Fe intensity and Ni intensity.Separately
Outside, in the figure 7, the time of measuring that horizontal axis expression is measured according to high frequency glow discharge emission spectrophotometer, the longitudinal axis represent to survey
The Fe intensity or Ni intensity measured.For example, in chart shown in Fig. 7, it, will be at the beginning of Fe intensity as starting point at the time of beginning using measuring
Secondary (being at the time of expression with " Fe intensity 1/10 " in the figure 7) at the time of become less than the 1/10 of maximum value is calculated as about 28sec
At the time of, thereby, it is possible to the thickness of Fe-Ni alloy layer 20a is acquired according to the time of measuring of about 28sec calculated.
In addition, for battery case surface treated steel plate 100b, it can also pass through high frequency glow discharge luminescence spectrometer point
Analysis apparatus measures the thickness of nickel coating 40.That is, for battery case surface treated steel plate 100b, sent out by high frequency glow discharge
Light spectroscopy apparatus measures the passage of Fe intensity to depth direction, can detect Fe intensity becomes less than maximum value 1/10
Thickness of the region as nickel coating 40.
Such as in chart shown in Fig. 7, as described above, to Fe intensity maximum value will be become less than for the first time since measurement
1/10 about 28sec at the time of until thickness of the depth as Fe-Ni alloy layer 20a, and will become from the Fe intensity
Fe intensity increases to more than the 1/10 of maximum value after declining at the time of about 28sec less than the 1/10 of maximum value to Fe intensity
Depth at the time of about 50sec until (be in the figure 7 by the use of " Fe intensity 1/10 " represent at the time of) is as the thickness of nickel coating 40.
At this point, based on from about 28sec at the time of about 22sec in during at the time of about 50sec time of measuring, nickel can be acquired
The thickness of coating 40.In addition, in battery case in surface treated steel plate 100b, as shown in fig. 7, reaching maximum than Fe intensity
Deeper partly there are iron-nickel diffusion layers 50 at the time of the about 50sec of more than 1/10 value.
But after the battery case for remaining nickel coating 40 is molded by the use of surface treated steel plate 100b as battery case, if
If battery case inner surface cracks deeper, crackle reaches steel plate 10, becomes steel plate 10, nickel coating 40 and iron-nickel diffusion layer
State as 50 exposures, then steel plate 10 be possible to easily dissolution in electrolyte.That is, in the situation for remaining nickel coating 40
Under, steel plate 10 and nickel coating 40 are poor there are standard electrode potential, result from this, pass through steel plate 10 and nickel coating 40 in the electrolytic solution
Battery is formed, iron is dissolved out from steel plate 10 and is diffused into electrolyte, it is possible to steel plate 10 is made continuously to be dissolved out.
In contrast, battery case shown in Fig. 3 does not remain nickel coating in surface treated steel plate 100a by making
40 structure compared with above-mentioned structure shown in fig. 6, can more efficiently prevent from the dissolution of steel plate 10.Therefore, in this embodiment party
In formula, as shown in figure 3, being preferably made to not remain the structure of nickel coating 40.
Here, as confirming in the battery case method that nickel coating 40 whether is remained in surface treated steel plate 100a,
Such as the method that Fe intensity is measured by high frequency glow discharge emission spectrophotometer can be included.That is, passing through high frequency
Glow discharge emission spectrophotometer measures Fe in a thickness direction from the Fe-Ni alloy layer 20a of most surface to steel plate 10
In the case of 1/10 region for becoming less than the maximum value of Fe intensity during the passage of intensity there are Fe intensity, it can be judged as residual
There are nickel coatings 40, on the other hand, in the case where becoming less than 1/10 region of maximum value there is no Fe intensity, can sentence
Break not remain nickel coating 40.
In particular, as shown in Figure 6, Figure 7, in battery case in surface treated steel plate 100b, since there are Fe intensity
1/10 region (in Fig. 7 from about 28sec to the region of about 50sec) of maximum value is become less than, therefore, it is possible to remain
Nickel coating 40.In addition, as shown in Fig. 3, Fig. 5, in battery case in surface treated steel plate 100a, there is no Fe intensity to become small
In 1/10 region of maximum value, can be judged as not remaining nickel coating 40.
3rd embodiment
Then, illustrate the 3rd embodiment of the present invention.
As shown in figure 8, in the battery case surface treated steel plate of the 3rd embodiment, sequentially formed on steel plate 10
Implement to be heat-treated after Fe-Ni alloy coating 30a and nickel coating 40a, make each layer thermal diffusion as a result, and will most surface layer be set as iron-
Nickel alloy layer manufactures battery case surface treated steel plate, in addition to this, passes through the electricity with the 1st embodiment shown in FIG. 1
Pond container is manufactured with the same method of surface treated steel plate, has same structure.
Here, the Fe-Ni alloy coating 30a formed on steel plate 10 can by with the iron of above first embodiment-
Plating is carried out under the conditions of nickel alloy plating is same and is formed, in addition, the nickel coating 40a being formed on steel plate 10 can be by adopting
It is bathed with watt, the well known method of sulfanilamide (SN) acid bath etc. is formed.
In the present embodiment, after by forming Fe-Ni alloy coating 30a and nickel coating 40a on steel plate 10, implement
It is heat-treated and forms Fe-Ni alloy layer, still, Fe-Ni alloy coating 30a and nickel coating 40a is made fully to spread at this time, until
Most surface is all formed with Fe-Ni alloy layer.
In addition, the condition to heat treatment is not particularly limited, it can be with the item of the heat treatment of above first embodiment
Part is similary, but can suitably adjust heat treatment temperature and heat treatment time, makes Fe-Ni alloy coating 30a and nickel coating 40a complete
Perfect diffusion, until most surface is all formed with Fe-Ni alloy layer.
In the present embodiment, the thickness of the nickel coating 40a before heat treatment is preferably 1.0 μm hereinafter, more preferably 0.5 μm
Below.By the way that the thickness of the nickel coating 40a before being heat-treated is set within the above range, will nickel coating can be made by heat treatment
Heat treatment temperature when 40a is fully spread is set as low temperature or can heat treatment time be set as the short time, therefore, it is possible to
It prevents from being deteriorated by thermally-induced steel plate 10.
In addition, in the present embodiment, the size of the average crystal grain diameter of the most surface of Fe-Ni alloy layer 20a with it is above-mentioned
The Fe-Ni alloy layer 20 of the battery case surface treated steel plate 100 of 1st embodiment is same.In addition, to control iron-
The method of the average crystal grain diameter of the most surface of nickel alloy layer is not particularly limited, but can for example include with it is above-mentioned
Implement the method for Fe-Ni alloy plating under the conditions of 1st embodiment is same, implement heat-treating methods.
Also, in the present embodiment, the hardness of Fe-Ni alloy layer is also used with the battery case of above first embodiment
The Fe-Ni alloy layer 20 of surface treated steel plate 100 is same.
To the thickness of Fe-Ni alloy layer, there is no particular limitation.Although in addition, to the Fe-Ni alloy coating before heat treatment
There is no particular limitation for the thickness of 30a, but preferably 0.5 μm~2.0 μm, more preferably 0.5 μm~1.5 μm.By by iron-nickel
The thickness of alloy layer 30a is set within the above range, when obtained battery case is used as battery case with surface treated steel plate
Battery case anti-leakage and battery behavior it is further up.
In the present embodiment, by foring the laggard of Fe-Ni alloy coating 30a and nickel coating 40a on steel plate 10
Row thermal diffusion, and make the size and above first embodiment of the average crystal grain diameter of the most surface of Fe-Ni alloy layer to be formed
Equally, it has the following effect.That is, first, when obtained battery case is used as battery case with surface treated steel plate, with
The battery case of above first embodiment similarly, can promote anti-leakage and battery behavior with surface treated steel plate 100.
In addition, in the battery case surface treated steel plate of present embodiment, become the Ni contained by Fe-Ni alloy layer
The ratio of atom highest near most surface, with being continuously decreased close to steel plate 10, thereby, it is possible to more effectively inhibit steel plate
The dissolution of iron in 10.In particular, first, the battery case of present embodiment surface treated steel plate is used as battery case
When, since the content of the Ni atoms of the most surface of Fe-Ni alloy layer is high, therefore, it is possible to effectively inhibit the dissolution of iron.Also,
When being molded as battery case, though battery case inner surface deeper occur cracking and steel plate 10 expose in the case of,
Since the comparision contents of the Ni atoms of side in Fe-Ni alloy layer, close to steel plate 10 are low, it can also reduce steel plate 10 and steel
The standard electrode potential of Fe-Ni alloy layer near plate 10 is poor, as a result, with as above-mentioned battery case shown in fig. 6 surface at
The structure that reason steel plate 100a remains nickel coating 40 like that is compared, and can more effectively inhibit the dissolution of the iron in steel plate 10.
In addition, as the Ni atoms for measuring battery case surface treated steel plate content than method, such as being capable of example
It enumerates and Ni intensity is measured from the Fe-Ni alloy layer of most surface to steel plate 10 by high frequency glow discharge emission spectrophotometer
The method of passage.
Embodiments of the present invention are this concludes the description of, but these embodiments are remembered to be readily appreciated that the present invention
It carries, is not intended to limit of the invention and record.Thus, each element disclosed in the above embodiment refers to, also includes
Belong to whole design alterations of the technical scope of the present invention, the meaning of equivalent.
Embodiment
Hereinafter, enumerating embodiment, the present invention is further illustrated, but the present invention is not limited to these embodiments.
In addition, each characteristic evaluation method is as follows.
The measurement ＞ of ＜ average crystal grain diameters
By using scanning type electricity Xian Wei Mirror (SEM), parse to battery case and penetrated with surface treated steel plate irradiation electronics
During line by by the surface of battery case surface treated steel plate reflect come electron ray project to screen obtained from after electronics
Reflection angle difference between adjacent point of irradiation is as a result, the region within 2 ° as a crystal grain by square scattering pattern (EBSD)
It is handled, calculates crystal grain diameter for each crystal grain, these results are averaged, so as to obtain battery case surface treated steel
The average crystal grain diameter of the most surface of plate.
＜ heat treatment after most surface Fe atoms content than measurement ＞
Pass through sweep type auger electrons spectroscopy apparatus (Japan Electronics Corporation's system, model：JAMP-9500F electricity) is measured
The surface of pond container surface treated steel plate obtains the content ratio (atom %) of Fe atoms.
The measurement ＞ of ＜ case hardnesses
By for battery case surface treated steel plate, by micro-hardness tester, (Co., Ltd.'s alum makes made, type
Number：MVK-G2) using diamond penetrator in load：10gf, retention time：Vickers hardness (HV) is measured under conditions of 10 seconds, is surveyed
Scale surface hardness.
The evaluation ＞ of ＜ battery behaviors
Battery case will be used to have taken care of 3 in the environment of 80 DEG C of temperature with the alkaline manganese battery that surface treated steel plate manufactures
It after it, connects galvanometer on battery and closed circuit is set, measure electric current (the short circuit electricity flowed between two-terminal at this time
Stream), according to obtained current value by following benchmark evaluation battery behavior.
A：Short circuit current is more than 9A
B：Short circuit current is more than 8A, less than 9A
C：Short circuit current is more than 7A, less than 8A
D：Short circuit current is less than 7A
In addition, in the evaluation of battery behavior, battery case surface treated steel of the short circuit current for more than 9A (evaluation A)
It is excellent that plate is judged as battery behavior, i.e., qualified, and short circuit current is less than the battery case surface treated steel of 9A (evaluation B~D)
Plate be judged as be used as battery case in the case of battery behavior it is poor, i.e., it is unqualified.
The evaluation ＞ of ＜ gas occurrence quantities
First, it is 3.9 Ω's using the alkaline manganese battery connection resistance value that battery case is manufactured with surface treated steel plate
External load is repeated a few days the operation of electric discharge 1 hour in 1 day, so as to which the voltage for making alkaline manganese battery drops to 0.4V.Later, will
After the alkaline manganese battery has taken care of 20 days in the environment of temperature 60 C, make its destruction in water, measure at this time in water
The amount of the gas of generation.According to following benchmark evaluation measurement result.
A：The amount of the gas of generation is less than 2cc
B：The amount of the gas of generation is more than 2cc, less than 2.5cc
C：The amount of the gas of generation is more than 2.5cc, less than 3cc
D：The amount of the gas of generation is more than 3cc
In addition, in gas generated evaluation result, the amount of the gas of generation is less than the battery appearance of 3cc (evaluation A, B)
It is longer that device with surface treated steel plate is judged as battery life when as battery case, i.e., qualified, the amount of the gas of generation is
The battery case of more than 2.5cc (evaluation C, D) is judged as that battery life is shorter in atomic battery container with surface treated steel plate,
It is i.e. unqualified.
《Embodiment 1》
As matrix, prepare the cold-reduced sheet (thickness of the low-carbon aluminium deoxidation killed steel with following shown chemical compositions
Steel plate obtained from 0.25mm) annealing.
C：0.045 weight %, Mn：0.23 weight %, Si：0.02 weight %, P：0.012 weight %, S：0.009 weight
Measure %, Al：0.063 weight %, remainder：Fe and inevitable impurity
Then, for ready steel plate, after alkaline electrolysis degreasing, the pickling of sulfuric acid dipping has been carried out, following
Under the conditions of carry out electrolysis plating, form the Fe-Ni alloy coating of 2 μm of thickness.In addition, following bath compositions are adjusted to what is formed
The composition of Fe-Ni alloy coating is content ratio 85% of the content than 15 atom % and Ni atoms of Fe atoms.In addition, in embodiment
In 1, coating is simply formed with the Fe-Ni alloy coating as upper strata coating.
Bath composition：Nickel sulfate 240g/L, nickel chloride 45g/L, ferric sulfate 10g/L, boric acid 30g/L
pH：3.0
Bath temperature：60℃
Current density：10A/dm2
Then, it by continuous annealing, under conditions of 700 DEG C of temperature, 1 minute, reducing atmosphere, is closed to being formed with iron-nickel
The steel plate of gold plate is heat-treated, and is made the thermal diffusion of Fe-Ni alloy coating and is formed Fe-Ni alloy layer, obtains knot shown in FIG. 1
The battery case surface treated steel plate of structure.
Then, for the battery case surface treated steel plate obtained in this way, average crystal grain is measured in accordance with above-mentioned method
The content ratio of the Fe atoms of most surface after diameter, heat treatment, case hardness.It the results are shown in table 1.
Also, blank diameter 57mm will be punched into surface treated steel plate in battery case obtained above, be closed with iron-nickel
Layer gold become battery case inner surface side mode implement drawing process several times, and then be molded by re-drawing, processing and forming into
Columnar LR6 types battery (single 3 type batteries) container of outer diameter 13.8mm, height 49.3mm, so as to make battery case.
Then, alkaline manganese battery is made as follows using obtained battery case.That is, by 10：1 ratio extraction is diacid
Manganese and graphite, addition mix potassium hydroxide (10mol/L) and make anode mixture.Then, which is added in a mold
The anode mixture particle of the ring-shaped of predetermined size is pressed and is shaped to, pressing is inserted into battery case obtained above.It connects
It, is inserted into a manner of the inner circumferential of anode mixture particle being inserted into battery case along pressing and is formed by vinylon woven fabric
Separator, will be by making cathode that the potassium hydroxide of oxidation zincification and zinc granule are formed gel-filled into battery case.Then,
Be welded with the gasket of installation insulator on the negative plate of cathode current collecting bar in point and carry out after being inserted into battery case riveting plus
Work, so as to make alkaline manganese battery.
Then, for the alkaline manganese battery obtained in this way, in accordance with above method evaluation battery behavior, gas generated.It will
As a result it is shown in Table 1 below.
《Embodiment 2~5》
Plating condition is changed, so that the composition of the Fe-Ni alloy coating (upper strata coating) formed by being electrolysed plating is such as
Shown in table 1, in addition to this, battery case surface treated steel plate and alkaline manganese battery are made similarly to Example 1, similarly
It is evaluated.It the results are shown in table 1.
《Comparative Examples 1 and 2》
Plating condition is changed, so that the composition of the Fe-Ni alloy coating (upper strata coating) formed by being electrolysed plating is such as
Shown in table 1, in addition to this, battery case surface treated steel plate and alkaline manganese battery are made similarly to Example 1, similarly
It is evaluated.It the results are shown in table 1.
《Comparative example 3》
The nickel coating of 2 μm of thickness is formd as upper strata coating by carrying out electrolysis plating under the following conditions to substitute
Fe-Ni alloy coating is stated, in addition to this, makes battery case surface treated steel plate and alkaline manganese electricity similarly to Example 1
Pond is carried out similarly evaluation.It the results are shown in table 1.
Bath composition：Nickel sulfate 250g/L, nickel chloride 45g/L, ferric sulfate 30g/L
pH：4.2
Bath temperature：60℃
Current density：10A/dm2
《Comparative example 4,5》
The thickness of the nickel coating (upper strata coating) formed by being electrolysed plating is set as shown in table 1, and shown in table 1
Under conditions of carry out box annealing and substitute the heat treatment carried out by above-mentioned continuous annealing, it is in addition to this, similary with comparative example 3
Ground makes battery case surface treated steel plate and alkaline manganese battery, is carried out similarly evaluation.It the results are shown in table 1.
[table 1]
* using A as qualification
* is using A and B as qualification * using A as qualification.
* is using A and B as qualification.
《Embodiment 6》
Under the following conditions, it forms the nickel coating (lower floor's coating) of 0.8 μm of thickness on the steel plate in advance, passes through electricity later
Electrolytic plating forms Fe-Ni alloy coating (upper strata coating) on the nickel coating, also, changes plating condition, so that the iron formed-
The composition and thickness of nickel alloy coating are as shown in table 2, and the battery for making the structure shown in Fig. 3 for not remaining nickel coating as a result, holds
In addition to this device surface treated steel plate, makes battery case surface treated steel plate and alkaline manganese electricity similarly to Example 1
Pond is carried out similarly evaluation.It the results are shown in table 2.In addition, in embodiment 6, as coating, Fe-Ni alloy plating is formed
Layer forms nickel coating as lower floor's coating as upper strata coating.
Bath composition：Nickel sulfate 250g/L, nickel chloride 45g/L, ferric sulfate 30g/L
pH：4.2
Bath temperature：60℃
Current density：10A/dm2
《Embodiment 7》
Plating condition is changed, so that the composition of the Fe-Ni alloy coating (upper strata coating) formed by being electrolysed plating is such as
Shown in table 2, in addition to this, the battery case surface treated steel plate and alkali of structure shown in Fig. 3 are made similarly to Example 6
Property manganese cell, is carried out similarly evaluation.It the results are shown in table 2.
In addition, in embodiment 6,7, nickel coating is confirmed not over above-mentioned high frequency glow discharge emission spectrophotometer
Residual, but the thickness ratio of the nickel coating due to being formed as lower floor's coating is relatively thin, it is therefore contemplated that obtained battery case surface
Handling steel plate becomes the structure shown in Fig. 3 for not remaining nickel coating.
Here, above-mentioned chart shown in fig. 5 by the thickness of lower floor's coating in addition to being set as 1.0 μm, the thickness by upper strata coating
It is set as except 1.0 μm, represents through high frequency glow discharge emission spectrophotometer to the battery that obtains similarly to Example 6
Container measures the result of Fe intensity and Ni intensity with surface treated steel plate.In the chart shown in fig. 5, as described above, not
There are 1/10 regions that Fe intensity becomes less than maximum value, can judge not residual in battery case surface treated steel plate
Stay nickel coating.Therefore, compared with the battery case surface treated steel plate in the chart of Fig. 5, subtract by the thickness of lower floor's coating
In thin to 0.8 μm of embodiment 6,7, nickel coating is more easily spread, and is plated it is therefore contemplated that becoming the nickel shown in Fig. 3 that do not remain
The battery case surface treated steel plate of the structure of layer.
《Embodiment 8,9》
Each plating condition is changed, so that the thickness for forming nickel coating (lower floor's coating) on the steel plate is as shown in table 2, and
And so that the composition and thickness of the Fe-Ni alloy coating (upper strata coating) being formed on the nickel coating are as shown in table 2, thus make
Make the battery case surface treated steel plate of the structure shown in fig. 6 for remaining nickel coating, in addition to this, similarly to Example 6
Ground makes battery case surface treated steel plate and alkaline manganese battery, is carried out similarly evaluation.It the results are shown in table 2.
In addition, in embodiment 8,9, for battery case surface treated steel plate, confirm by the way that following method is practical,
And the remaining evaluation of nickel coating is carried out.That is, carry out such evaluate：Pass through high frequency glow discharge emission spectrophotometer
(Rigaku societies system, model：GDS-3860) Ni intensity is measured in a thickness direction towards steel plate from the Fe-Ni alloy layer of most surface
During with the passage of Fe intensity, 1/10 region of the maximum value of Fe intensity is become less than if there is Fe intensity, then is judged as residual
There are nickel coatings, on the other hand, 1/10 region of maximum value are become less than if there is no Fe intensity, then is judged as not residual
Stay nickel coating.The result of embodiment 8 is represented in (A) of Fig. 9, the result of embodiment 9 is illustrated respectively in (B) of Fig. 9.
(A) in Fig. 9, in (B) of Fig. 9, Fe intensity becomes less than the 1/ of maximum value in the region shown in single dotted broken line
10, it is able to confirm that out individualism nickel.It is possible thereby to confirming the structure of the battery case surface treated steel plate of embodiment 8,9 is
The structure shown in fig. 6 for remaining nickel coating.
[table 2]
* using A as qualification.
* is using A and B as qualification
* using A as qualification.
* is using A and B as qualification.
《Embodiment 10》
On the steel plate, with by be electrolysed plating formed Fe-Ni alloy coating (lower floor's coating) form and thickness such as table 3
Shown mode, after foring Fe-Ni alloy coating, and then on the Fe-Ni alloy coating formed 0.1 μm of thickness nickel coating
(upper strata coating), and be heat-treated, make Fe-Ni alloy coating and nickel coating thermal diffusion as a result, and formed Fe-Ni alloy layer from
And the battery case surface treated steel plate of structure shown in FIG. 1 has been made, in addition to this, electricity is made similarly to Example 1
Pond container surface treated steel plate and alkaline manganese battery, are carried out similarly evaluation.It the results are shown in table 3.In addition, implementing
In example 10, as coating, nickel coating is formed as upper strata coating, forms Fe-Ni alloy coating as lower floor's coating.
《Embodiment 11》
Plating condition is changed, so that the composition of the Fe-Ni alloy coating (lower floor's coating) formed by being electrolysed plating is such as
Shown in table 3, in addition to this, battery case surface treated steel plate and alkaline manganese battery are made similarly to Example 10, equally
It is evaluated on ground.It the results are shown in table 3.
《Comparative example 6》
Other than the form that the thickness for being formed in the nickel coating (upper strata coating) on most surface layer is set as shown in table 3, with than
Battery case surface treated steel plate and alkaline manganese battery are similarly made compared with example 3, is carried out similarly evaluation.It the results are shown in
In table 3.
《Comparative example 7》
Plating condition is changed, so that the composition of Fe-Ni alloy coating (lower floor's coating) formed to pass through electrolysis plating
As shown in table 3, in addition to this, battery case surface treated steel plate and alkaline manganese battery are made similarly to Example 10, together
Evaluated to sample.It the results are shown in table 3.
[table 3]
* using A as qualification
* is using A and B as qualification.
* using A as qualification.
* is using A and B as qualification.
As shown in Table 1 to Table 3, the embodiment 1 that the average crystal grain diameter of the most surface of Fe-Ni alloy layer is 1 μm~8 μm~
The evaluation result of 11 battery behavior is good, and the battery behaviors such as flash-over characteristic are excellent.Also, the gas hair of embodiment 1~11
The evaluation result of raw amount is good, and battery life is longer.
In contrast, as shown in table 1, table 3, the average crystal grain diameter of the most surface of Fe-Ni alloy layer is less than 1 μm or is more than
The evaluation result of the battery behavior of 8 μm of comparative example 1,3~7 is poor, and the battery behaviors such as flash-over characteristic are poor.In addition, iron-nickel
The average crystal grain diameter of the most surface of alloy-layer is less than the evaluation knot of the gas occurrence quantity of 1 μm or the comparative example 2,4,7 more than 8 μm
Fruit is poor, and battery life is shorter.
Reference sign
100th, 100a, 100b, battery case surface treated steel plate；10th, steel plate；20th, 20a, Fe-Ni alloy layer；30、
30a, Fe-Ni alloy coating；40th, 40a, nickel coating；50th, iron-nickel diffusion layer.
Claims (5)
1. a kind of battery case surface treated steel plate, which is characterized in that
The battery case is that implementation is heat-treated after implementing Fe-Ni alloy plating on the steel plate with surface treated steel plate
, wherein,
Most surface layer is Fe-Ni alloy layer,
The average crystal grain diameter of the most surface of the Fe-Ni alloy layer is 1 μm~8 μm.
2. battery case surface treated steel plate according to claim 1, which is characterized in that
The content ratio of the Fe atoms of the most surface of the Fe-Ni alloy layer is the atom % of 12 atom %~50.
3. battery case surface treated steel plate according to claim 1 or 2, which is characterized in that
The Vickers hardness (HV) of the Fe-Ni alloy layer is 210~250.
4. a kind of battery case, wherein, which is by battery case table according to any one of claims 1 to 3
Surface treatment steel plate carries out what processing and forming formed.
5. a kind of battery, wherein, which formed using the battery case described in claim 4.
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| JP2013-158573 | 2013-07-31 | ||
| JP2013158573A JP6292789B2 (en) | 2013-07-31 | 2013-07-31 | Surface-treated steel sheet for battery container, battery container and battery |
| PCT/JP2014/061020 WO2015015846A1 (en) | 2013-07-31 | 2014-04-18 | Surface-treated steel sheet for use as battery casing, battery casing, and battery |
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| JP (1) | JP6292789B2 (en) |
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| US20220010450A1 (en) | 2018-12-27 | 2022-01-13 | Nippon Steel Corporation | Ni-COATED STEEL SHEET HAVING EXCELLENT CORROSION RESISTANCE AFTER WORKING AND METHOD FOR MANUFACTURING Ni-COATED STEEL SHEET |
| KR102477435B1 (en) * | 2020-12-09 | 2022-12-15 | 주식회사 티씨씨스틸 | Nickel plated heat treated steel sheet having excellent processaibility and manufacturing method thereof |
| KR102514058B1 (en) | 2021-05-20 | 2023-03-28 | 주식회사 티씨씨스틸 | Nickel plated stainless steel sheet having excellent processaibility and manufacturing method thereof |
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| US4200515A (en) * | 1979-01-16 | 1980-04-29 | The International Nickel Company, Inc. | Sintered metal powder-coated electrodes for water electrolysis prepared with polysilicate-based paints |
| CN1262789A (en) * | 1997-07-08 | 2000-08-09 | 东洋钢板株式会社 | Surface-treated steel sheet for battery case, battery case, and battery manufactured by using case |
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| JP2785902B2 (en) * | 1993-06-04 | 1998-08-13 | 片山特殊工業株式会社 | Material for forming battery can and battery can using the material |
| TW338071B (en) * | 1996-05-09 | 1998-08-11 | Toyo Koban Kk | A battery container and surface treated steel sheet for battery container |
| JPH10212595A (en) * | 1998-03-06 | 1998-08-11 | Katayama Tokushu Kogyo Kk | Manufacture of battery can forming material and battery can made of the same forming material |
| JP4130989B2 (en) | 1998-08-10 | 2008-08-13 | 東芝電池株式会社 | Alkaline battery |
| JP2006190648A (en) * | 2004-12-10 | 2006-07-20 | Toyo Kohan Co Ltd | Plated sheet steel for battery case, battery case using the plated sheet steel for battery case, and battery using the battery case |
| JP4983095B2 (en) | 2006-05-23 | 2012-07-25 | トヨタ自動車株式会社 | Alkaline storage battery and manufacturing method thereof |
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- 2013-07-31 JP JP2013158573A patent/JP6292789B2/en active Active
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- 2014-04-18 CN CN201480043048.9A patent/CN105431959B/en active Active
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| US4200515A (en) * | 1979-01-16 | 1980-04-29 | The International Nickel Company, Inc. | Sintered metal powder-coated electrodes for water electrolysis prepared with polysilicate-based paints |
| CN1262789A (en) * | 1997-07-08 | 2000-08-09 | 东洋钢板株式会社 | Surface-treated steel sheet for battery case, battery case, and battery manufactured by using case |
| CN1311829A (en) * | 1998-07-24 | 2001-09-05 | 东洋钢钣株式会社 | Surface treated steel sheet for battery case, method for prodn. thereof, battery case formed by the steel sheet |
| CN101180748A (en) * | 2005-06-22 | 2008-05-14 | 松下电器产业株式会社 | Battery can and method for manufacturing same |
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| JP6292789B2 (en) | 2018-03-14 |
| US9887396B2 (en) | 2018-02-06 |
| CN105431959A (en) | 2016-03-23 |
| KR102216706B1 (en) | 2021-02-16 |
| JP2015032346A (en) | 2015-02-16 |
| KR20160037845A (en) | 2016-04-06 |
| WO2015015846A1 (en) | 2015-02-05 |
| US20160211489A1 (en) | 2016-07-21 |
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